6-Amino-1,3-dimethyl-5-[(E)-2-(methyl-sulfan-yl)benzyl-idene-amino]-pyrimidine-2,4(1H,3H)-dione.

The title compound, C(14)H(16)N(4)O(2)S, is a Schiff base derivative of 2-(methyl-sulfan-yl)benzaldehyde. The configuration about the C=N double bond is E. The heterocyclic ring is essentially planar (τ = 3.1°) and makes a dihedral angle of 12.24 (7)° with the benzene ring. An intra-molecular N-H⋯S hydrogen bond is observed. In the crystal, N-H⋯O and C-H⋯O hydrogen bonds link mol-ecules into layers perpendicular to [101]. The closest distance between the centroids of two heterocyclic rings was found to be 3.5268 (8) Å.

Related literature

For background on chelating ligands, see: Gade (1998 ▶). For the crystal structures of other Schiff bases derived from ortho-(thio­meth­yl)benzaldehyde, see: Yan et al. (2007 ▶); Baidina et al. (1987 ▶). For details of graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶). For details of puckering analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C14H16N4O2S

M = 304.37

Monoclinic,

a = 7.9740 (2) Å

b = 12.4630 (3) Å

c = 13.9870 (3) Å

β = 94.384 (1)°

V = 1385.96 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.24 mm−1

T = 100 K

0.45 × 0.25 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer

13383 measured reflections

3441 independent reflections

2912 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.094

S = 1.09

3441 reflections

201 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811020903/wn2434sup1.cif

Supplementary material file. DOI: 10.1107/S1600536811020903/wn2434Isup2.cdx

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811020903/wn2434Isup3.hkl

Supplementary material file. DOI: 10.1107/S1600536811020903/wn2434Isup4.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H16N4O2S	F(000) = 640
Mr = 304.37	Dx = 1.459 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 6560 reflections
a = 7.9740 (2) Å	θ = 2.6–28.3°
b = 12.4630 (3) Å	µ = 0.24 mm−1
c = 13.9870 (3) Å	T = 100 K
β = 94.384 (1)°	Rod, yellow
V = 1385.96 (6) Å3	0.45 × 0.25 × 0.13 mm
Z = 4

Bruker APEXII CCD diffractometer	2912 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
graphite	θmax = 28.3°, θmin = 2.2°
φ and ω scans	h = −10→10
13383 measured reflections	k = −16→16
3441 independent reflections	l = −17→18

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.042P)2 + 0.7103P] where P = (Fo2 + 2Fc2)/3
3441 reflections	(Δ/σ)max < 0.001
201 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

	x	y	z	Uiso*/Ueq
S1	0.24479 (5)	0.11449 (3)	0.01927 (3)	0.01828 (10)
O1	0.20013 (13)	0.57346 (8)	0.04281 (7)	0.0182 (2)
O2	0.45091 (14)	0.64532 (9)	−0.23229 (8)	0.0219 (2)
N1	0.32410 (15)	0.60885 (9)	−0.09573 (8)	0.0145 (2)
N2	0.45428 (15)	0.47261 (10)	−0.17925 (8)	0.0151 (2)
N3	0.26375 (15)	0.34072 (10)	0.01660 (8)	0.0141 (2)
N4	0.43846 (16)	0.29401 (11)	−0.13145 (9)	0.0179 (3)
H741	0.392 (3)	0.2487 (17)	−0.0927 (14)	0.027 (5)*
H742	0.480 (3)	0.2713 (18)	−0.1826 (16)	0.039 (6)*
C1	0.31118 (17)	0.42673 (11)	−0.03962 (9)	0.0133 (3)
C2	0.27303 (17)	0.53685 (11)	−0.02460 (10)	0.0131 (3)
C3	0.41138 (17)	0.58028 (12)	−0.17251 (10)	0.0155 (3)
C4	0.40082 (17)	0.39688 (11)	−0.11738 (10)	0.0142 (3)
C5	0.19312 (18)	0.35231 (11)	0.09502 (10)	0.0164 (3)
H5	0.1728	0.4229	0.1171	0.020*
C6	0.14235 (18)	0.26118 (12)	0.15205 (10)	0.0148 (3)
C7	0.15496 (18)	0.15166 (12)	0.12645 (10)	0.0155 (3)
C8	0.09458 (18)	0.07399 (12)	0.18772 (11)	0.0187 (3)
H8	0.1007	0.0003	0.1709	0.022*
C9	0.02593 (19)	0.10237 (13)	0.27252 (11)	0.0203 (3)
H9	−0.0145	0.0482	0.3126	0.024*
C10	0.01599 (19)	0.20918 (13)	0.29904 (11)	0.0201 (3)
H10	−0.0300	0.2284	0.3573	0.024*
C11	0.07393 (17)	0.28749 (12)	0.23952 (10)	0.0151 (3)
H11	0.0676	0.3607	0.2579	0.018*
C12	0.2959 (2)	0.72400 (11)	−0.08308 (11)	0.0193 (3)
H121	0.4043	0.7604	−0.0708	0.029*
H122	0.2275	0.7352	−0.0286	0.029*
H123	0.2370	0.7534	−0.1413	0.029*
C13	0.55971 (19)	0.44007 (13)	−0.25572 (10)	0.0203 (3)
H131	0.6549	0.3976	−0.2282	0.030*
H132	0.6017	0.5041	−0.2869	0.030*
H133	0.4929	0.3968	−0.3032	0.030*
C14	0.2462 (2)	−0.03061 (12)	0.02441 (12)	0.0259 (3)
H141	0.3075	−0.0541	0.0842	0.039*
H142	0.3016	−0.0591	−0.0304	0.039*
H143	0.1303	−0.0572	0.0222	0.039*

	U11	U22	U33	U12	U13	U23
S1	0.0251 (2)	0.01325 (17)	0.01737 (18)	−0.00195 (13)	0.00745 (13)	−0.00143 (13)
O1	0.0237 (5)	0.0156 (5)	0.0163 (5)	0.0005 (4)	0.0081 (4)	−0.0011 (4)
O2	0.0257 (6)	0.0225 (6)	0.0184 (5)	−0.0023 (4)	0.0070 (4)	0.0074 (4)
N1	0.0171 (6)	0.0121 (6)	0.0145 (5)	−0.0006 (4)	0.0034 (4)	0.0017 (4)
N2	0.0155 (6)	0.0186 (6)	0.0120 (5)	−0.0005 (5)	0.0056 (4)	−0.0005 (4)
N3	0.0153 (6)	0.0126 (6)	0.0147 (6)	−0.0011 (4)	0.0016 (4)	0.0001 (4)
N4	0.0217 (6)	0.0167 (6)	0.0161 (6)	0.0006 (5)	0.0079 (5)	−0.0031 (5)
C1	0.0154 (6)	0.0117 (6)	0.0130 (6)	−0.0011 (5)	0.0027 (5)	−0.0003 (5)
C2	0.0142 (6)	0.0128 (6)	0.0125 (6)	−0.0016 (5)	0.0018 (5)	0.0005 (5)
C3	0.0145 (6)	0.0186 (7)	0.0134 (6)	−0.0017 (5)	0.0016 (5)	0.0018 (5)
C4	0.0141 (6)	0.0149 (7)	0.0135 (6)	−0.0015 (5)	0.0007 (5)	−0.0013 (5)
C5	0.0194 (7)	0.0130 (6)	0.0174 (7)	0.0008 (5)	0.0046 (5)	0.0000 (5)
C6	0.0144 (7)	0.0160 (7)	0.0143 (6)	−0.0002 (5)	0.0034 (5)	0.0007 (5)
C7	0.0148 (6)	0.0166 (7)	0.0151 (6)	−0.0012 (5)	0.0025 (5)	0.0012 (5)
C8	0.0196 (7)	0.0159 (7)	0.0207 (7)	−0.0034 (5)	0.0029 (6)	0.0032 (6)
C9	0.0187 (7)	0.0234 (8)	0.0192 (7)	−0.0042 (6)	0.0039 (6)	0.0072 (6)
C10	0.0184 (7)	0.0262 (8)	0.0162 (7)	−0.0009 (6)	0.0052 (5)	0.0031 (6)
C11	0.0161 (7)	0.0162 (7)	0.0136 (6)	0.0006 (5)	0.0058 (5)	0.0016 (5)
C12	0.0239 (8)	0.0114 (6)	0.0228 (7)	0.0009 (5)	0.0030 (6)	0.0028 (5)
C13	0.0209 (7)	0.0253 (8)	0.0160 (7)	−0.0004 (6)	0.0103 (6)	−0.0009 (6)
C14	0.0373 (9)	0.0130 (7)	0.0284 (8)	−0.0009 (6)	0.0095 (7)	−0.0030 (6)

S1—C7	1.7719 (15)	C6—C11	1.4157 (19)
S1—C14	1.8098 (16)	C6—C7	1.417 (2)
O1—C2	1.2325 (17)	C7—C8	1.402 (2)
O2—C3	1.2231 (17)	C8—C9	1.390 (2)
N1—C3	1.3706 (18)	C8—H8	0.9500
N1—C2	1.4223 (17)	C9—C10	1.386 (2)
N1—C12	1.4655 (18)	C9—H9	0.9500
N2—C4	1.3702 (18)	C10—C11	1.385 (2)
N2—C3	1.3897 (19)	C10—H10	0.9500
N2—C13	1.4672 (17)	C11—H11	0.9500
N3—C5	1.2789 (18)	C12—H121	0.9800
N3—C1	1.3986 (18)	C12—H122	0.9800
N4—C4	1.3348 (19)	C12—H123	0.9800
N4—H741	0.88 (2)	C13—H131	0.9800
N4—H742	0.86 (2)	C13—H132	0.9800
C1—C4	1.3968 (19)	C13—H133	0.9800
C1—C2	1.4247 (19)	C14—H141	0.9800
C5—C6	1.463 (2)	C14—H142	0.9800
C5—H5	0.9500	C14—H143	0.9800
C7—S1—C14	103.25 (7)	C6—C7—S1	120.46 (11)
C3—N1—C2	125.02 (12)	C9—C8—C7	121.47 (14)
C3—N1—C12	116.16 (12)	C9—C8—H8	119.3
C2—N1—C12	118.59 (11)	C7—C8—H8	119.3
C4—N2—C3	122.15 (12)	C10—C9—C8	120.49 (14)
C4—N2—C13	119.56 (12)	C10—C9—H9	119.8
C3—N2—C13	118.29 (12)	C8—C9—H9	119.8
C5—N3—C1	123.47 (13)	C11—C10—C9	119.18 (14)
C4—N4—H741	114.4 (13)	C11—C10—H10	120.4
C4—N4—H742	123.0 (15)	C9—C10—H10	120.4
H741—N4—H742	120 (2)	C10—C11—C6	121.64 (14)
C4—C1—N3	114.22 (12)	C10—C11—H11	119.2
C4—C1—C2	119.94 (12)	C6—C11—H11	119.2
N3—C1—C2	125.83 (12)	N1—C12—H121	109.5
O1—C2—N1	118.60 (12)	N1—C12—H122	109.5
O1—C2—C1	126.01 (13)	H121—C12—H122	109.5
N1—C2—C1	115.39 (12)	N1—C12—H123	109.5
O2—C3—N1	122.42 (14)	H121—C12—H123	109.5
O2—C3—N2	121.06 (13)	H122—C12—H123	109.5
N1—C3—N2	116.51 (12)	N2—C13—H131	109.5
N4—C4—N2	118.96 (13)	N2—C13—H132	109.5
N4—C4—C1	120.31 (13)	H131—C13—H132	109.5
N2—C4—C1	120.71 (13)	N2—C13—H133	109.5
N3—C5—C6	122.58 (13)	H131—C13—H133	109.5
N3—C5—H5	118.7	H132—C13—H133	109.5
C6—C5—H5	118.7	S1—C14—H141	109.5
C11—C6—C7	118.76 (13)	S1—C14—H142	109.5
C11—C6—C5	115.63 (13)	H141—C14—H142	109.5
C7—C6—C5	125.61 (13)	S1—C14—H143	109.5
C8—C7—C6	118.44 (13)	H141—C14—H143	109.5
C8—C7—S1	121.10 (12)	H142—C14—H143	109.5
C5—N3—C1—C4	174.13 (13)	C13—N2—C4—C1	175.11 (13)
C5—N3—C1—C2	−7.2 (2)	N3—C1—C4—N4	−1.84 (19)
C3—N1—C2—O1	177.49 (13)	C2—C1—C4—N4	179.37 (13)
C12—N1—C2—O1	3.22 (19)	N3—C1—C4—N2	179.44 (12)
C3—N1—C2—C1	−3.08 (19)	C2—C1—C4—N2	0.6 (2)
C12—N1—C2—C1	−177.34 (12)	C1—N3—C5—C6	179.11 (13)
C4—C1—C2—O1	−177.39 (14)	N3—C5—C6—C11	176.78 (13)
N3—C1—C2—O1	4.0 (2)	N3—C5—C6—C7	−3.8 (2)
C4—C1—C2—N1	3.22 (19)	C11—C6—C7—C8	1.8 (2)
N3—C1—C2—N1	−175.42 (12)	C5—C6—C7—C8	−177.64 (14)
C2—N1—C3—O2	179.26 (13)	C11—C6—C7—S1	−178.33 (11)
C12—N1—C3—O2	−6.3 (2)	C5—C6—C7—S1	2.3 (2)
C2—N1—C3—N2	−1.0 (2)	C14—S1—C7—C8	−4.30 (14)
C12—N1—C3—N2	173.35 (12)	C14—S1—C7—C6	175.81 (12)
C4—N2—C3—O2	−175.03 (13)	C6—C7—C8—C9	−1.0 (2)
C13—N2—C3—O2	4.7 (2)	S1—C7—C8—C9	179.16 (11)
C4—N2—C3—N1	5.27 (19)	C7—C8—C9—C10	−0.3 (2)
C13—N2—C3—N1	−175.01 (12)	C8—C9—C10—C11	0.6 (2)
C3—N2—C4—N4	176.08 (13)	C9—C10—C11—C6	0.3 (2)
C13—N2—C4—N4	−3.6 (2)	C7—C6—C11—C10	−1.5 (2)
C3—N2—C4—C1	−5.2 (2)	C5—C6—C11—C10	177.98 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H741···S1	0.88 (2)	2.63 (2)	3.5117 (14)	178.4 (17)
N4—H742···O2i	0.86 (2)	2.07 (2)	2.8463 (16)	150 (2)
C9—H9···O1ii	0.95	2.61	3.2807 (18)	128.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H741⋯S1	0.88 (2)	2.63 (2)	3.5117 (14)	178.4 (17)
N4—H742⋯O2i	0.86 (2)	2.07 (2)	2.8463 (16)	150 (2)
C9—H9⋯O1ii	0.95	2.61	3.2807 (18)	128

Symmetry codes: (i) ; (ii) .